U.S. patent number 6,121,219 [Application Number 09/371,231] was granted by the patent office on 2000-09-19 for antimicrobial acid cleaner for use on organic or food soil.
This patent grant is currently assigned to Ecolab Inc.. Invention is credited to David A. Halsrud, Brandon L. Herdt.
United States Patent |
6,121,219 |
Herdt , et al. |
September 19, 2000 |
**Please see images for:
( Certificate of Correction ) ** |
Antimicrobial acid cleaner for use on organic or food soil
Abstract
The invention relates to compositions and methods for cleaning
typically organic beverage and food soils. The cleaning composition
is formulated to remove carbohydrate and proteinaceous soils from
hard surfaces. The formulations of the invention are directed to
remove carbohydrate and proteinaceous soils from beverage
manufacturing locations such as soils arising in the manufacture of
malt beverages, fruit juices, dairy products, etc.
Inventors: |
Herdt; Brandon L. (Newport,
MN), Halsrud; David A. (Minneapolis, MN) |
Assignee: |
Ecolab Inc. (St. Paul,
MN)
|
Family
ID: |
23050748 |
Appl.
No.: |
09/371,231 |
Filed: |
August 10, 1999 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
Issue Date |
|
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275065 |
Mar 23, 1999 |
5998358 |
|
|
|
Current U.S.
Class: |
510/218; 510/253;
510/269; 510/286; 510/319; 510/342; 510/382; 510/384; 510/405;
510/432; 510/434; 510/436; 510/453; 510/467; 510/477; 510/504;
510/534 |
Current CPC
Class: |
C11D
1/42 (20130101); C11D 3/0026 (20130101); C11D
3/2075 (20130101); C11D 3/30 (20130101); C11D
3/36 (20130101); C11D 3/43 (20130101); C11D
7/5022 (20130101); C11D 7/08 (20130101); C11D
7/261 (20130101); C11D 7/263 (20130101); C11D
7/265 (20130101); C11D 7/3227 (20130101); C11D
7/36 (20130101); C11D 3/48 (20130101) |
Current International
Class: |
C11D
3/36 (20060101); C11D 3/00 (20060101); C11D
7/22 (20060101); C11D 7/50 (20060101); C11D
3/30 (20060101); C11D 7/08 (20060101); C11D
3/26 (20060101); C11D 3/20 (20060101); C11D
7/32 (20060101); C11D 3/43 (20060101); C11D
3/48 (20060101); C11D 7/36 (20060101); C11D
7/02 (20060101); C11D 7/26 (20060101); C11D
001/62 (); C11D 007/08 (); C11D 003/43 () |
Field of
Search: |
;510/218,253,269,286,319,342,382,384,405,434,453,432,436,467,477,504,534 |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Gupta; Yogendra
Assistant Examiner: Boyer; Charles
Attorney, Agent or Firm: Merchant & Gould P.C.
Parent Case Text
This application is a division of application Ser. No. 09/275,065
filed Mar. 23, 1999, now U.S. Pat. No. 5,998,358.
Claims
What is claimed is:
1. A low foaming acid cleaner composition, the composition
comprising:
(a) about 1 to 80 wt % of phosphoric acid
(b) about 0.1 to 40 wt % of an organic carboxylic acid;
(c) about 0.1 to 40 wt % of a solvent comprising a hydrocarbon
ether functional group and a hydrocarbon alcohol functional
group;
(d) about 0.1 to 40 wt % of a phosphonate sequestrant; and
(e) about 0.1 to 40 wt % of a quartemary amine composition
comprising the formula:
wherein X is halogen or sulfate and one or two of R.sub.1, R.sub.2,
R.sub.3 and R.sub.4 are independently organic C.sub.6 -C.sub.22
alkyl, alkyl phenyl or alkyl benzyl, and all others are C.sub.1
-C.sub.4 alkyl;
wherein the composition has a pH of less than 5 and can remove
either carbohydrate or proteinaceous soil from hard surfaces.
2. The formula of claim 1 wherein the organic acid comprises lactic
acid, gluconic acid, citric acid, hydroxyacetic acid or mixtures
thereof.
3. The composition of claim 1 wherein the solvent comprises a
C.sub.1-6 lower alkanol or a C.sub.1-6 alkyl cellosolve.
4. The composition of claim 1 wherein the solvent comprises a
C.sub.1-6 lower alkanol.
5. The composition of claim 1 wherein the solvent comprises a
ethylene glycol mono-C.sub.1-6 -alkyl ether.
6. The method of claim 1 wherein the solvent comprises a compound
of the formula:
wherein R.sub.1 is a C.sub.1-24 alkyl group, R.sub.2 is a C.sub.1-6
alkylene group and n is a number of 1 to 3.
7. The composition of claim 1 wherein the phosphonate comprises an
amino-(trimethylene phosphonic acid) or salt thereof.
8. A clean-in-place method of cleaning a beverage manufacturing
unit, said method capable of removing carbohydrate and
proteinaceous soils, said method comprising the steps of:
(a) contacting containers and conduits in a beverage manufacturing
unit with a cleaning composition comprising:
(i) about 1 to 40 wt % of phosphoric acid
(ii) about 0.01 to 10 wt % of an organic carboxylic acid;
(iii) about 0.01 to 10 wt % of a solvent comprising a hydrocarbon
ether functional group and a hydrocarbon alcohol functional
group;
(iv) about 0.01 to 10 wt % of a phosphonate sequestrant; and
(v) about 0.01 to 10 wt % of a quartemary amine composition
comprising the formula:
wherein X.sup.- is halogen or sulfate and one or two of R.sub.1,
R.sub.2, R.sub.3 and R.sub.4 are independently organic C.sub.6-22
alkyl, alkyl phenyl, alkyl benzyl, and all others are C.sub.1
-C.sub.4 alkyl;
wherein the composition has a pH of less than 5 and is contacted
with a manufacturing unit for sufficient period of time to remove
carbohydrate or proteinaceous soils; and
(b) removing the composition from the manufacturing unit for the
purpose of reinitiating beverage manufacture.
9. The method of claim 1 wherein the cleaning composition is free
of a surfactant composition and the organic acid comprises lactic
acid, gluconic acid, citric acid, hydroxyacetic acid or mixtures
thereof.
10. The composition of claim 1 wherein the solvent comprises a
blend of a C.sub.1-6 lower alkanol and a C.sub.1-6 alkyl
cellosolve.
11. The composition of claim 1 wherein the solvent comprises a
C.sub.1-6 lower alkanol.
12. The composition of claim 1 wherein the solvent comprises a
ethylene glycol mono-C.sub.1-6 -alkyl ether.
13. The method of claim 1 wherein the phosphonate comprises an
amino-(trimethylene phosphonic acid) or salt thereof.
Description
FIELD OF THE INVENTION
The invention relates to acid cleaning compositions formulated for
organic soil removal or, more particularly, for food soil removal.
Further, the invention relates to cleaning processes for the
purpose of removing carbohydrate and proteinaceous soils from
beverage manufacturing locations using a clean-in-place method. The
cleaning compositions of the invention are formulated in an aqueous
acid system and are directed to removing carbohydrate and
proteinaceous soils from a hard surface.
BACKGROUND OF THE INVENTION
In the manufacture of foods and beverages, hard surfaces commonly
become contaminated with carbohydrate, proteinaceous, hardness
soils and other soils. Such soils can arise from the manufacture of
both liquid and solid foodstuffs. Carbohydrate soils including
cellulosics, monosaccharides, disaccharides, oligosaccharides,
starches, gums and other complex materials, when dried, can form
tough, hard to remove soils particularly when combined with other
soil types. Similarly, other materials arising from foodstuffs
including proteins, enzymes, fats and oils can also form
contaminating, hard to remove soil, residues. One particular
problem in the manufacture of beverages such as malt beverages,
fruit juices such a citrus products, dairy products and others, can
be the removal of largely carbohydrate soils that can also contain
other soil components such as proteins, enzymes, fats, oils and
others. The removal of such carbohydrate soils can be a significant
problem.
Prior art compositions formulated for soil removal include various
disclosures relating to acid cleaners containing a formulated
detergent composition. Casey, U.S. Pat. No. 4,587,030 discloses a
composition formulated to remove soap scum and hardness components
using an aqueous base containing a surfactant system, and
formulations of an amine oxide and cosolvent. Reihm et al., U.S.
Pat. No. 4,699,728 discloses a fiberglass cleaner composition
containing an organophosphonic acid/acrylic acid sequestrant in
combination with a betaine surfactant. Heinhuis-Walther et al.,
U.S. Pat. No. 5,000,867 discloses a disinfectant composition
comprising quaternary ammonium antimicrobials combined with organic
and/or inorganic acids. Oaks et al, U.S. Pat. No. 5,437,868
discloses acidic peroxyacid antimicrobial compositions that can be
formulated with functional materials. Gorin et al., U.S. Pat. No.
5,712,241 discloses a light duty liquid detergent containing a
specific surfactant system. Ihns et al., U.S. Pat. No. 5,861,366
discloses soil removing agents containing an enzyme in formulations
specifically designed to enhance proteolytic soil removal.
In formulating effective cleaning materials, formulators are
constrained by available low cost materials, the use of materials
that provide useful properties and compatibility and stability of
the ingredients used. Combining acidic materials, and other
materials such as enzymes can pose stability problems for the
active materials. Further, obtaining cleaning and bactericidal
effectiveness including a sanitizing effect is difficult for common
formulator applications. Many of the formulations in the prior art
have stability limitations or do not provide sufficient cleaning
and sanitizing to be effective in the clean-in-place food or
beverage applications.
Clean-in-place cleaning techniques are a specific cleaning regimen
adapted for removing soils from the internal components of tanks,
lines, pumps and other process equipment used for processing
typically liquid product streams such as beverages, milk, juices,
etc. Clean-in-place cleaning involves passing cleaning solutions
through the system without dismantling any system components. The
minimum clean-in-place technique involves passing the cleaning
solution through the equipment and then resuming normal processing.
Any product contaminated by cleaner residue can be discarded. Often
clean-in-place methods involve a first rinse, the application of
the cleaning solutions, a second rinse with potable water followed
by resumed operations. The process can also include any other
contacting step in which a rinse, acidic or basic functional fluid,
solvent or other cleaning component such as hot water, cold water,
etc. can be contacted with the equipment at any step during the
process. Often the final potable water rinse is skipped in order to
prevent contamination of the equipment with bacteria following the
cleaning sanitizing step. The formulations of the invention that
can be used in the clean-in-place technique typically comprise a
mineral acid optionally in combination with an organic acid, a
hydrocarbon ether solvent or a hydrocarbon alcohol solvent, a
sequestrant composition, an ether amine composition and a variety
of surfactant materials.
A substantial need exists for improved soil removal detergents and
methods
using acidic formulations. Further, a substantial need exists for
compositions and methods for removing soil from hard surfaces such
as conduits, tanks and pumps used in beverage manufacture using a
clean-in-place technique.
BRIEF DISCUSSION OF THE INVENTION
We have found improved acid formulations that have enhanced
capacity for the removal of common food soils in a method to clean
hard surfaces in a CIP regimen. Further, we have found a method for
removing carbohydrate and other food soil residues from beverage
manufacturing equipment using clean-in-place techniques. The
compositions must include a food grade or food compatible acid, a
solvent material and either an ether amine or a quaternary ammonium
compound. The unique compositions of the invention comprise an acid
source such as a food grade mineral acid including phosphoric acid,
sulfamic acid, hydroxy carboxylic acids, etc. The formulations also
contain a solvent system comprising a lower alkanol or alkyl ether
lower alcohol solvent, a sequestrant composition, an alkyl ether
amine composition and other optional ingredients such as added
acid, other surfactant ingredients, phosphonate surfactants, added
solvent and other compositions. Formulations without surfactant can
clean surprisingly well. These materials can be used in an acid
aqueous solution and can be contacted with hard surfaces for soil
removal. These compositions are particularly effective in removing
carbohydrate soils from beverage locations using a clean-in-place
technique. When used in food preparation, conduits, tanks, pumps,
lines and other components of beverage manufacturing units can
rapidly be contaminated with carbohydrate soils. These soils can be
rapidly removed using the compositions of the invention. Typically,
the compositions of the invention are contacted with the beverage
manufacturing unit and are directed through the lines, tanks,
conduits, pumps, etc. of the manufacturing unit removing
carbohydrate soils until the unit is substantially residue free.
Once the compositions have removed harmful soil residues, the
compositions are removed from the manufacturing unit and beverage
production is re-initiated. If necessary, a rinse step can be
utilized between the cleaning step and beverage manufacture.
Alternatively, beverage manufacture can be re-initiated using the
beverage to remove clean residue from the system, discarding
contaminated beverage.
DETAILED DISCUSSION OF THE INVENTION
Briefly, the acidic cleaning compositions of this invention are
formed from a major proportion of water, a food grade or food
compatable acidic component comprising an inorganic acid or organic
acid or combinations thereof. The acidic component used to prepare
the acidic compositions of the invention that can be dissolved in
the aqueous organic cosolvent system of the invention to produce an
acidic pH in the range of about 1 to 5. A pH substantially less
than about 1 can result in substantial corrosion of metal and other
surfaces common in the cleaning environment, while a pH greater
than about 5 can unacceptably reduce the cleaning efficiency of the
composition.
Most common commercially-available inorganic and organic acids can
be used in the invention. Examples of useful inorganic acids
include phosphoric acid and sulfamic acid. Useful weak organic
acids include acetic acid, hydroxyacetic acid, glycolic acid,
citric acid, benzoic acid, tartaric acid and the like. I have found
in many applications that a mixture of a weak organic and a weak
inorganic acid in the composition can result in a surprising
increase in cleaning efficacy. Preferred cleaning systems comprise
the combination of an organic acid such as citric acid, acetic
acid, or hydroxyacetic acid (glycolic acid) and phosphoric acid.
The most preferred acid cleaning system comprises either lactic
acid or phosphoric acid.
In the case of phosphoric acid-lactic acid systems, the weight
ratio of phosphoric acid to hydroxyacetic acid is preferably about
15:1 to 1:1, most preferably about 8-1.5:1. I have found that one
type of difficult soil to remove from surfaces appears to be
carbohydrate soils that can be contaminated with proteinaceous
soils and inorganic soils such as CaHPO.sub.4, etc. This component
is part of many soils and can be a result of the interaction
between hardness components and acid-containing cleaners using
phosphoric acid as the acidic component. We believe a mixture of
lactic acid with the phosphoric acid in the acidic cleaner can
optimize cleaning properties. However, in some locales, the
phosphate content permitted in cleansing compositions is restricted
or must be limited to a negligible amount.
Water conditioning agents function to inactivate water hardness and
prevent calcium and magnesium ions from interacting with soils,
surfactants, carbonate and hydroxide. Water conditioning agents
therefore improve detergency and prevent long term effects such as
insoluble soil redepositions, mineral scales and mixtures thereof.
Water conditioning can be achieved by different mechanisms
including sequestration, precipitation, ion-exchange and dispersion
(threshold effect). Metal ions such as calcium and magnesium do not
exist in aqueous solution as simple positively charged ions.
Because they have a positive charge, they tend to surround
themselves with water molecules and become solvated. Other
molecules or anionic groups are also capable of being attracted by
metallic cations. When these moieties replace water molecules, the
resulting metal complexes are called coordination compounds. An
atom, ion or molecule that combines with a central metal ion is
called a ligand or complexing agent. A type of coordination
compound in which a central metal ion is attached by coordinate
links to two or more nonmetal atoms of the same molecule is called
a chelate. A molecule capable of forming coordination complexes
because of its structure and ionic charge is termed a chelating
agent. Since the chelating agent is attached to the same metal ion
at two or more complexing sites, a heterocyclic ring that includes
the metal ions is formed. The binding between the metal ion and the
liquid may vary with the reactants; but, whether the binding is
ionic, covalent or hydrogen bonding, the function of the ligands is
to donate electrons to the metal.
Ligands form both water soluble and water insoluble chelates. When
a ligand forms a stable water soluble chelate, the ligand is said
to be a sequestering agent and the metal is sequestered.
Sequestration therefore, is the phenomenon of typing up metal ions
in soluble complexes, thereby preventing the formation of
undesirable precipitates. The builder should combine with calcium
and magnesium to form soluble, but undissociated complexes that
remain in solution in the presence of precipitating anions.
Examples of water conditioning agents which employ this mechanism
are the condensed phosphates, glassy polyphosphates, phosphonates,
amino polyacetates. and hydroxycarboxylic acid salts and
derivatives. Like ligands which inactivate metal ions by
precipitation, similar effect is achieved by simple supersaturation
of calcium and magnesium salts having low solubility. Typically
carbonates and hydroxides achieve water conditioning by
precipitation of calcium and magnesium as respective salts.
Orthophosphate is another example of a water conditioning agent
which precipitates water hardness ions. Once precipitated, the
metal ions are inactivated.
Water conditioning can also be affected by an in situ exchange of
hardness ions from the detersive water solution to a solid (ion
exchanger) incorporated as an ingredient in the detergent. In
detergent art, this ion exchanger is an aluminosilicate of
amorphoric or crystalline structure and of naturally occurring or
synthetic origin commercially designated as zeolite. To function
properly, the zeolite must be of small particle size of about 0.1
to about 10 microns in diameter for maximum surface exposure and
kinetic ion exchange. The water conditioning mechanisms of
precipitation, sequestration and ion exchange are stoichiometric
interactions requiring specific mass action proportions of water
conditioner to calcium and magnesium ion concentrations. Certain
sequestering agents can further control hardness ions at
sub-stoichiometric concentrations. This property is called the
"threshold effect" and is explained by an adsorption of the agent
onto the active growth sites of the submicroscopic crystal nuclei
which are initially produced in the supersaturated hard water
solution, i.e., calcium and magnesium salts. This completely
prevents crystal growth, or at least delays growth of these crystal
nuclei for a long period of time. In addition, threshold agents
reduce the agglomeration of crystallites already formed. Compounds
which display both sequestering and threshold phenomena with water
hardness minerals are much preferred conditioning agents for employ
in the present invention. Examples include tripolyphosphate and the
glassy polyphosphates, phosphonates, and certain homopolymers and
copolymer salts of carboxylic acids. Often these compounds are used
in conjunction with the other types of water conditioning agents
for enhanced performance. Combinations of water conditioners having
different mechanisms of interaction with hardness result in binary,
ternary or even more complex conditioning systems providing
improved detersive activity.
The water conditioning agents which can be employed in the
detergent compositions of the present invention can be inorganic or
organic in nature; and, water soluble or water insoluble at use
dilution concentrations. Useful examples include all physical forms
of alkali metal, ammonium and substituted ammonium salts of
carbonate, bicarbonate and sesquicarbonate; pyrophrophates, and
condensed polyphosphates such as tripolyphosphate, trimetaphosphate
and ring open derivatives; and, glassy polymeric metaphosphates of
general structure M.sub.n+2 P.sub.n O.sub.3n+1 having a degree of
polymerization n of from about 6 to about 21 in anhydrous or
hydrated forms; and, mixtures thereof.
Aluminosilicate builders are useful in the present invention.
Useful aluminosilicate ion exchange materials are commercially
available. These aluminosilicates can be amorphous or crystalline
in structure and can be naturally-occurring aluminosilicates or
synthetically derived.
Organic water soluble water conditioning agents useful in the
compositions of the present invention include aminpolyacetates,
polyphosphonates, aminopolyphosphonates, short chain carboxylates
and a wide variety of polycarboxylate compounds. Organic water
conditioning agents can generally be added to the composition in
acid form and neutralized in situ; but, can also be added in the
form of a pre-neutralized salt. When utilized in salt form, alkali
metals such as sodium, potassium and lithium; or, substituted
ammonium salts such as from mono-, di- or triethanolammonium
cations are generally preferred.
Polyphosphonates useful herein specifically include the sodium,
lithium and potassium salts of ethylene diphosphonic acid; sodium,
lithium and potassium salts of ethane-1-hydroxy-1,1-diphosphonic
acid and sodium lithium, potassium, ammonium and substituted
ammonium salts of ethane-2-carboxy-1,1-diphosphonic acid,
amino-(trimethylenephosphonic acid) and salts thereof,
hydroxymethanediphosphonic acid, carbonyldiphosphonic acid,
ethane-1-hydroxy-1,1,2-triphosphonic acid,
ethane-2-hydroxy-1,1,2-triphosphonic acid,
propane-1,1,3,3-tetraphosphonic acid
propane-1,1,2,3-tetraphosphonic acid and propane
1,2,2,3-tetraphosphonic acid; and mixtures thereof Examples of
these polyphosphonic compounds are disclosed in British Pat. No.
1,026,366. For more examples see U.S. Pat. No. 3,213,030 to Diehl
issued Oct. 19, 1965 and U.S. Pat. No. 2,599,807 to Bersworth
issued Jun. 10, 1952.
The water soluble aminopolyphosphonic acids, or salts thereof,
compounds are excellent water conditioning agents and may be
advantageously used in the present invention. Suitable examples
include soluble salts, e.g. sodium, lithium or potassium salts, of
amino-(trimethylenephosphonic acid) diethylene diamine
pentamethylene phosphonic acid, ethylene diamine tetramethylene
phosphonic acid, hexamethylenediamine tetramethylene phosphonic
acid, and nitrilotrimethylene phosphonic acid; and, mixtures
thereof. Water soluble short chain carboxylic acid salts constitute
another class of water conditioner for use herein. Examples include
citric acid, gluconic acid and phytic acid. Preferred salts are
prepared from alkali metal ions such as sodium, potassium, lithium
and from ammonium and substituted ammonium.
Suitable water soluble polycarboxylate water conditioners for this
invention include the various ether polycarboxylates, polyacetal,
polycarboxylates, epoxy polycarboxylates, and aliphatic-,
cycloalkane- and aromatic polycarboxylates. Greater detail is
disclosed in U.S. Pat. No. 3,635,830 to Lamberti et al. issued Jan.
18, 1972, incorporated herein by reference. Water soluble
polyacetal carboxylic acids or salts thereof which are useful
herein as water conditioners are generally described in U.S. Pat.
No. 4,144,226 to Crutchfield et al. issued Mar. 13, 1979 and U.S.
Pat. No. 4,315,092 to Crutchfield et al. issued Feb. 9, 1982.
Water soluble polymeric aliphatic carboxylic acids and salts
preferred for application are compositions of this invention are
selected from the groups consisting of:
(a) a water soluble salts of homopolymers of aliphatic
polycarboxylic acids
(b) water soluble salts of copolymers of at least two of the
monomeric species having the empirical formula described in (a),
and
(c) water soluble salts of copolymers of a member selected from the
group of alkylenes and monocarboxylic acids with the aliphatic
polycarboxylic compounds
The most preferred water conditioner for use in the most preferred
embodiments of this invention are water soluble polymers of acrylic
acid, acrylic acid copolymers; and derivatives and salts
thereof.
Such polymers include polyacrylic acid, polymethacrylic acid,
acrylic acid-methacrylic acid copolymers, hydrolyzed
polyacrylamide, hydrolyzed polymethacrylamide, hydrolyzed
acrylamidemethacrylamide copolymers, hydrolyzed polyacrylonitrile,
hydrolyzed polymethacrylonitrile, hydrolyzed
acrylonitrilemethacrylonitrile copolymers, or mixtures thereof
Water soluble salts or partial salts of these polymers such as the
respective alkali metal (e.g. sodium, lithium potassium) or
ammonium and ammonium derivative salts can also be used. The weight
average molecular weight of the polymers is from about 500 to about
15,000 and is preferably within the range of from 750 to 10,000.
Preferred polymers include polyacrylic acid, the partial sodium
salt of polyacrylic acid or sodium polyacrylate having weight
average molecular weights within the range of 1,000 to 5,000 or
6,000. These polymers are commercially available, and methods for
their preparation are well-known in the art.
For example, commercially available polyacrylate solutions useful
in the present cleaning compositions include the sodium
polyacrylate solution, Colloid.RTM. 207 (Colloids, Inc., Newark,
N.J.); the polyacrylic acid solution, Aquatreat.RTM. AR-602-A (Alco
Chemical Corp., Chattanooga, Tenn.); the polyacrylic acid solutions
(50-65% solids) and the sodium polyacrylate powers (M.W. 2,100 and
6,000) and solutions (45% solids) available as the Goodrite.RTM.
K-700 series from B.F. Goodrich Co.; and the sodium or partial
sodium salts of polyacrylic acid solutions (M.W. 1000 to 4500)
available as the Acusol.RTM. series from Rohm and Haas. Of course
combinations and admixtures of any of the above enumerated water
conditioning agents may be advantageously utilized within the
embodiments of the present invention.
Generally, the concentration of water or conditioner mixture useful
in use dilution, solutions of the present invention ranges from
about 0.0005% (5 ppm) by active weight to about 0.04% (400 ppm) by
active weight, preferably from about 0.001% (10 ppm) by active
weight to about 0.03% (300 ppm) by active weight, and most
preferably from about 0.002% (20 ppm) by weight to about 0.02% (200
ppm) by active weight.
The concentration of water or conditioner mixture usefull in the
most preferred concentrated embodiment of the present invention
ranges from about 1.0% by active weight to about 35% by active
weight of the total formula weight percent of the builder
containing composition.
Also commonly used are polyols containing only carbon, hydrogen and
oxygen atoms. They preferably contain from about 2 to about 6
carbon atoms and from about 2 to about 6 hydroxy groups. Examples
include 1,2-propanediol, 1,2-butanediol, hexylene glycol, glycerol,
sorbitol, mannitol, and glucose. Nonaqueous liquid carrier or
solvents can be used for varying compositions of the present
invention. These include the higher glycols,
polyglycols, polyoxides and glycol ethers. Suitable substances are
alkyl ether alcohols such as methoxyethanol, methoxyethanol
acetate, butyoxy ethanol (butyl cellosolve), propylene glycol,
polyethylene glycol, polypropylene glycol, diethylene glycol
monoethyl ether, diethylene glycol monopropyl ether, diethylene
glycol monobutyl ether, tripropylene glycol methyl ether, propylene
glycol methyl ether (PM), dipropylene glycol methyl ether (DPM),
propylene glycol methyl ether acetate (PMA), dipropylene glycol
methyl ether acetate (CPMA), ethylene glycol n-butyl ether,
1,2-dimethoxyethane, 2-ethoxy ethanol, 2-ethoxy-ethylacetate,
phenoxy ethanol, and ethylene glycol n-propyl ether. Other useful
solvents are ethylene oxide/propylene oxide, liquid random
copolymer such as Synalox.RTM. solvent series from Dow Chemical
(e.g., Synalox.RTM. 50-50B). Other suitable solvents are propylene
glycol ethers such as PnB, DpnB and TpnB (propylene glycol mono
n-butyl ether, dipropylene glycol and tripropylene glycol mono
n-butyl ethers sold by Dow Chemical under the trade name
Dowanol.RTM.. Also tripropylene glycol mono methyl ether "TPM
Dowanol.RTM." from Dow Chemical is suitable.
The aqueous cleaners of the invention comprises an amine compound.
The amine compound functions to enhance compositional cleaning,
further antimicrobial character, and reduce or eliminate the
formation of various precipitates resulting from the dilution of
water and/or contaminants on the surface of application.
The amine compounds of the invention may comprise any number of
species. Preferably, the amine compound is an alkyl ether amine
compound of the formulae.
and mixtures thereof, wherein R.sub.1 may be a linear saturated or
unsaturated C.sub.6-18 alkyl, R.sub.2 may be a linear or branched
C.sub.1-8 alkyl, and R.sub.3 may be a linear or branched C.sub.1-8
alkyl. More preferably, R.sub.1 is a linear C.sub.12-16 alkyl;
R.sub.2 is a C.sub.2-6 linear or branched alkyl; and R.sub.3 is a
C.sub.2-6 linear or branched alkyl.
Preferred compositions of the invention include linear alkyl ether
diamine compounds of formula (2) wherein R is C.sub.12-16, R.sub.2
is C.sub.2-4, and R.sub.3 is C.sub.2-4 alkyl. When the amine
compound used is an amine of formulas (1) and (2), R.sub.1 is
either a linear alkyl C.sub.12-16 or a mixture of linear alkyl
C.sub.10-12 and C.sub.14-16. Overall the linear alkyl ether amine
compounds used in the composition of the invention provide lower
use concentrations, upon dilution, with enhanced soil removal. The
amount of the amine compound in the concentrate generally ranges
from about 0.1 wt-% to 90 wt-%, preferably about 0.25 wt-% to 75
wt-%, and more preferably about 0.5 wt-% to 50 wt-%. These
materials are commercially available from Tomah Products
Incorporated as PA-10, PA-19, PA-1618, PA-1816, DA-18, DA-19,
DA-1618, DA-1816, and the like.
The use dilution of the concentrate is preferably calculated to get
disinfectant or sanitizing efficacy in the intended application or
use. Accordingly, the active amine compound concentration in the
composition of the invention ranges from about 10 ppm to 10000 ppm,
preferably from about 20 ppm to 7500 ppm, and most preferably about
40 ppm to 5000 ppm.
As a substitute for all or a part of the ether amine compound
described above, quaternary ammonium compounds can be used.
Suitable quaternary compounds include generally the quaternary
ammonium salt compounds which may be described as containing, in
addition to the usual halide (chloride, bromide, iodide, etc.),
sulfate, phosphate, or other anion, aliphatic and/or alicyclic
radicals, preferably aldyl and/or aralkyl, bonded through carbon
atoms therein to the remaining 4 available positions of the
nitrogen atom, 2 or 3 of which radicals may be joined to form a
heterocycle with the nitrogen atom, at least one of such radicals
being aliphatic with at least 8, up to 22 or more, carbon
atoms.
Suitable agents which may be incorporated are quaternary ammonium
salts of the formula:
wherein at least one, but not more than two, of R.sub.1, R.sub.2,
R.sub.3, and R.sub.4 is an organic radical containing a group
selected from a C.sub.16 -C.sub.22 aliphatic radical, or an alkyl
phenyl or alkyl benzyl radical having 10-16 atoms in the alkyl
chain, the remaining group or groups being selected from
hydrocarbyl groups containing from 1 to about 4 carbon atoms, or
C.sub.2 -C.sub.4 hydroxyl alkyl groups and cyclic structures in
which the nitrogen atom forms part of the ring, and Y is an anion
such as halide, methylsulphate, or ethylsulphate.
In the context of the above definition, the hydrophobic moiety
(i.e. the C.sub.16 -C.sub.22 aliphatic, C.sub.10 -C.sub.16 alklyl
phenyl or alkyl benzyl radical) in the organic radical R.sub.1 may
be directly attached to the quaternary nitrogen atom or may be
indirectly attached thereto through an amide, esters, alkoxy,
ether, or like grouping.
The quaternary ammonium agents can be prepared in various ways well
known in the art. Many such materials are commercially
available.
As illustrative of such cationic detergents, there may be mentioned
distearyl dimethyl ammonium chloride, stearyl dimethyl benzyl
ammonium chloride, coconut alkyl dimethyl benzyl ammonium chloride,
dicoconut alkyl dimethyl ammonium bromide, cetyl pyridinium iodide,
and cetyl pyridinium iodide, and cetyl trimethyl ammonium bromide
and the like.
An ample description of useful quaternary compounds appears in
McCutcheon's "Detergents and Emulsifiers", 1969 Annual, and in
"Surface Active Agents" by Schwartz, Perry and Berch, Vol. 11, 1958
(Interscience Publishers), which descriptions are incorporated
herein by reference.
The particular surfactant or surfactant mixture chosen for use in
the process and products of this invention depends upon the
conditions of final utility, including method of manufacture,
physical product form, use pH, use temperature, foam control, and
soil type. The preferred surfactant system of the invention is
selected from nonionic surfactant types. Anionics are incompatible
and precipitate in these systems. Nonionic surfactants offer
diverse and comprehensive commercial selection, low price; and,
most important, excellent detersive effect--meaning surface
wetting, soil penetration, soil removal from the surface being
cleaned, and soil suspension in the detergent solution. This
preference does not suggest exclusion of utility for cationics, or
for that sub-class of nonionic entitled semi-polar nonionics, or
for those surface-active agents which are characterized by
persistent cationic and anionic double ion behavior, thus differing
from classical amphoteric, and which are classified as zwitterionic
surfactants.
One skilled in the art will understand that inclusion of cationic,
semi-polar nonionic, or zwitterionic surfactants; or, mixtures
thereof will impart beneficial and/or differentiating utility to
various embodiments of the present invention. As example, foam
stabilization for detersive compositions designed to be foamed onto
equipment or environmental floor, wall and ceiling surfaces; or,
gel development for products dispensed as a clinging thin gel onto
soiled surfaces; or, for antimicrobial preservation; or, for
corrosion prevention--and so forth.
The most preferred surfactant system of the present invention is
selected from nonionic surface-active agent classes, or mixtures
thereof that impart low foam to the use-dilution, use solution of
the detergent composition during application. Preferably, the
surfactant or the individual surfactants participating within the
surfactant mixture are of themselves low foaming within normal use
concentrations and within expected operational application
parameters of the detergent composition and cleaning program. In
practice, however, there is advantage to blending low foaming
surfactants with higher foaming surfactants because the latter
often impart superior detersive properties to the detergent
composition. Mixtures of low foam and high foam nonionics and
mixtures of low foam nonionics can be useful in the present
invention if the foam profile of the combination is low foaming at
normal use conditions. Thus high foaming nonionics can be
judiciously employed in low or moderate foam systems without
departing from the spirit of this invention.
Particularly preferred concentrate embodiments of this invention
are designed for clean-in-place (CIP) cleaning systems within food
process facilities; and, most particularly for beverage, malt
beverage, juice, dairy farm and fluid milk and milk by-product
producers. Foam is a major concern in these highly agitated, pump
recirculation systems during the cleaning program. Excessive foam
reduces flow rate, cavitates recirculation pumps, inhibits
detersive solution contact with soiled surfaces, and prolongs
drainage. Such occurrences during CIP operations adversely affect
cleaning performance and sanitizing efficiencies.
Low foaming is therefore a descriptive detergent characteristic
broadly defined as a quantity of foam which does not manifest any
of the problems enumerated above when the detergent is incorporated
into the cleaning program of a CIP system. Because no foam is the
ideal, the issue becomes that of determining what is the maximum
level or quantity of foam which can be tolerated within the CIP
system without causing observable mechanical or detersive
disruption; and, then commercializing only formulas having foam
profiles at least below this maximum; but, more practically,
significantly below this maximum for assurance of optimum detersive
performance and CIP system operation.
Acceptable foam levels in CIP systems have been empirically
determined in practice by trial and error. Obviously, commercial
products exist today which meet the low foam profile needs of CIP
operation. It is therefore, a relatively straightforward task to
employ such commercial products as standards for comparison and to
establish laboratory foam evaluation devices and test methods which
simulate, if not duplicate, CIP program conditions, i.e. agitation,
temperature, and concentration parameters.
In practice, the present invention permits incorporation of high
concentrations of surfactant as compared to conventional
chlorinated, high alkaline CIP and COP cleaners. Certain preferred
surfactant or surfactant mixtures of the invention are not
generally physically compatible nor chemically stable with the
alkalis and chlorine of convention. This major differentiation from
the art necessitates not only careful foam profile analysis of
surfactants being included into compositions of the invention; but,
also demands critical scrutiny of their detersive properties of
soil removal and suspension. The present invention relies upon the
surfactant system for gross soil removal from equipment surfaces
and for soil suspension in the detersive solution. Soil suspension
is as important a surfactant property in CIP detersive systems as
soil removal to prevent soil redeposition on cleaned surfaces
during recirculation and later re-use in CIP systems which save and
re-employ the same detersive solution again for several cleaning
cycles. Generally, the concentration of surfactant or surfactant
mixture useful in use-dilution, use solutions of the present
invention ranges from about 0.002% (20 ppm) by weight to about 2%
(20,000 ppm) by weight, preferably from about 0.005% (50 ppm) by
weight to about 0.1% (1000 ppm) by weight, and most preferably from
about 0.05% (500 ppm) by weight to about 0.005% (50 ppm) by
weight.
The concentration of surfactant or surfactant mixture useful in the
most preferred concentrated embodiment of the present invention
ranges from about 5% by weight to about 75% by weight of the total
formula weight percent of the enzyme containing composition.
A typical listing of the classes and species of surfactants useful
herein appears in U.S. Pat. No. 3,664,961 issued May 23, 1972, to
Norris, incorporated herein by reference. Nonionic Surfactants,
edited by Schick, M. J., Vol. 1 of the Surfactant Science Series,
Marcel Dekker, Inc., New York, 1983 is an excellent reference on
the wide variety of nonionic compounds generally employed in the
practice of the present invention. Nonionic surfactants useful in
the invention are generally characterized by the presence of an
organic hydrophobic group and an organic hydrophilic group and are
typically produced by the condensation of an organic aliphatic,
alkyl aromatic or polyoxyalkylene hydrophobic compound with a
hydrophilic alkaline oxide moiety which in common practice is
ethylene oxide or a polyhydration product thereof, polyethylene
glycol. Practically any hydrophobic compound having a hydroxyl,
carboxyl, amino, or amido group with a reactive hydrogen atom can
be condensed with ethylene oxide, or its polyhydration adducts, or
its mixtures with alkoxylenes such as propylene oxide to form a
nonionic surface-active agent. The length of the hydrophilic
polyoxyalkylene moiety which is condensed with any particular
hydrophobic compound can be readily adjusted to yield a water
dispersible or water soluble compound having the desired degree of
balance between hydrophilic and hydrophobic properties. Useful
nonionic surfactants in the present invention include block
polyoxypropylenepolyoxyethylene polymeric compounds based upon
propylene glycol, ethylene glycol, glycerol, trimethylolpropane,
and ethylenediamine as the initiator reactive hydrogen compound.
Condensation products of one mole of alkyl phenol wherein the alkyl
chain, of straight chain or branched chain configuration, or of
single or dual alkyl constituent, contains from about 8 to about 18
carbon atoms with from about 3 to about 50 moles of ethylene oxide.
The alkyl group can, for example, be represented by diisobutylene,
di-amyl, polymerized propylene, iso-octyl, nonyl, and di-nonyl.
Examples of commercial compounds of this chemistry are available on
the market under the trade name Igepal.RTM. manufactured by
Rhone-Poulenc and Triton.RTM. manufactured by Union Carbide.
Condensation products of one mole of a saturated or unsaturated,
straight or branched chain alcohol having from about 6 to about 24
carbon atoms with from about 3 to about 50 moles of ethylene oxide.
The alcohol moiety can consist of mixtures of alcohols in the above
delineated carbon range or it can consist of an alcohol having a
specific number of carbon atoms within this range. Examples of like
commercial surfactant are available under the trade name
Neodol.RTM. manufactured by Shell Chemical Co. and Alfonic.RTM.
manufactured by Vista Chemical Co. Low foaming alkoxylated
nonionics are preferred although other higher foaming alkoxylated
nonionics can be used without departing from the spirit of this
invention if used in conjunction with low foaming agents so as to
control the foam profile of the mixture within the detergent
composition as a whole. Examples of nonionic low foaming
surfactants include:
Nonionics that are modified by "capping" or "end blocking" the
terminal hydroxy group or groups (of multi-functional moieties) to
reduce foaming by reaction with a small hydrophobic molecule such
as propylene oxide, butylene oxide, benzyl chloride; and, short
chain fatty acids, alcohols or alkyl halides containing from 1 to
about 5 carbon atoms; and mixtures thereof. Also included are
reactants such as thionyl chloride which convert terminal hydroxy
groups to a chloride group. Such modifications to the terminal
hydroxy group may lead to all-block, block-heteric, heteric-block
or all-heteric nonionics.
The polyalkylene glycol condensates of U.S. Pat. No. 3,048,548
issued Aug. 7, 1962 to Martin et al., hereby incorporated by
reference, having alternating hydrophilic oxyethylene chains and
hydrophobic oxypropylene chains where the weight of the terminal
hydrophobic chains, the weight of the middle hydrophobic unit and
the weight of the linking hydrophilic units each represent about
one-third of the condensate.
The defoaming nonionic surfactants disclosed in U.S. Pat. No.
3,382,178 issued May 7, 1968 to Lissant et al., incorporated herein
by reference, having the general formula Z[(OR).sub.n OH].sub.z
wherein Z is alkoxylatable material, R is a radical derived from an
alkaline oxide which can be ethylene and propylene and n is an
integer from, for example, 10 to 2,000 or more and z is an integer
determined by the number of reactive oxyalkylatable groups.
The conjugated polyoxyalkylene compounds described in U.S. Pat. No.
2,677,700, issued May 4, 1954 to Jackson et al., incorporated
herein by reference, corresponding to the formula Y(C.sub.3 H.sub.6
O).sub.n (C.sub.2 H.sub.4 O).sub.m H wherein Y is the residue of
organic compound having from about 1 to 6 carbon atoms and one
reactive hydrogen atom, n has an average value of at least about
6.4, as determined by hydroxyl number and m has a value such that
the oxyethylene portion constitutes about 10% to about 90% by
weight of the molecule.
The conjugated polyoxyalkylene compounds described in U.S. Pat.
No.
2,674,619, issued Apr. 6, 1954 to Lundsted et al, incorporated
herein by reference, having the formula Y[(C.sub.3 H.sub.6 O).sub.n
(C.sub.2 H.sub.4 O).sub.m H].sub.x wherein Y is the residue of an
organic compound having from about 2 to 6 carbon atoms and
containing x reactive hydrogen atoms in which x has a value of at
least about 2, n has a value such that the molecular weight of the
polyoxypropylene hydrophobic base is at least about 900 and m has
value such that the oxyethylene content of the molecule is from
about 10% to about 90% by weight. Compounds falling within the
scope of the definition for Y include, for example, propylene
glycol, glycerin, pentaerythritol, trimethylolpropane,
ethylenediamine and the like. The oxypropylene chains optionally,
but advantageously, contain small amounts of ethylene oxide and the
oxyethylene chains also optionally, but advantageously, contain
small amounts of propylene oxide.
Additional conjugated polyoxyalkylene surface-active agents which
are advantageously used in the compositions of this invention
correspond to the formula: P[(C.sub.3 H.sub.6 O).sub.n (C.sub.2
H.sub.4 O).sub.m H].sub.x wherein P is the residue of an organic
compound having from about 8 to 18 carbon atoms and containing x
reactive hydrogen atoms in which x has a value of 1 or 2, n has a
value such that the molecular weight of the polyoxyethylene portion
is at least about 44 and m has a value such that the oxypropylene
content of the molecule is from about 10% to about 90% by weight.
In either case the oxypropylene chains may contain optionally, but
advantageously, small amounts of ethylene oxide and the oxyethylene
chains may contain also optionally, but advantageously, small
amounts of propylene oxide. Another nonionic can comprise a silicon
surfactant of the invention that comprises a modified dialkyl,
preferably a dimethyl polysiloxane. The polysiloxane hydrophobic
group is modified with one or more pendent hydrophilic polyalkylene
oxide group or groups. Such surfactants provide low surface
tension, high wetting, antifoaming and excellent stain removal.
We have found that the silicone nonionic surfactants of the
invention, in a detergent composition with another nonionic
surfactant can reduce the surface tension of the aqueous solutions,
made by dispensing the detergent with an aqueous spray, to between
about 35 and 15 dynes/centimeter, preferably between 30 and 15
dynes/centimeter. The silicone surfactants of the invention
comprise a polydialkyl siloxane, preferably a polydimethyl siloxane
to which polyether, typically polyethylene oxide, groups have been
grafted through a hydrosilation reaction. The process results in an
alkyl pendent (AP type) copolymer, in which the polyalkylene oxide
groups are attached along the siloxane backbone through a series of
hydrolytically stable Si--C bond.
These nonionic substituted poly dialkyl siloxane products have the
following generic formula: ##STR1## wherein PE represents a
nonionic group, preferably --CH.sub.2 --(CH.sub.2).sub.p
--O--(EO).sub.m (PO).sub.n --Z, EO representing ethylene oxide, PO
representing propylene oxide, x is a number that ranges from about
0 to about 100, y is a number that ranges from about 1 to 100, m, n
and p are numbers that range from about 0 to about 50, m+n.gtoreq.1
and Z represents hydrogen or R wherein each R independently
represents a lower (C.sub.1-6) straight or branched alkyl.
A second class of nonionic silicone surfactants is an
alkoxy-end-blocked (AEB type) that are less preferred because the
Si--O-- bond offers limited resistance to hydrolysis under neutral
or slightly alkaline conditions, but breaks down quickly in acidic
environments. Another useful surfactant is sold under the
SILWET.RTM. trademark or under the ABIL.RTM. B trademark. One
preferred surfactant, SILWET.RTM. L77, has the formula:
wherein R.sup.1 =--CH.sub.2 CH.sub.2 CH.sub.2 --O--[CH.sub.2
CH.sub.2 O].sub.z CH.sub.3 ; wherein z is 4 to 16 preferably 4 to
12, most preferably 7-9. The surfactant or surfactant admixture of
the present invention can be selected from water soluble or water
dispersible nonionic, semi-polar nonionic, anionic, cationic,
amphoteric, or zwitterionic surface-active agents; or any
combination thereof.
Surface active substances are classified as cationic if the charge
on the hydrotrope portion of the molecule is positive. Surfactants
in which the hydrotrope carries no charge unless the pH is lowered
close to neutrality or lower are also included in this group (e.g.
alkyl amines). In theory, cationic surfactants may be synthesized
from any combination of elements containing an "onium" structure
RnX.sup.+ Y.sup.- and could include compounds other than nitrogen
(ammonium) such as phosphorus (phosphonium) and sulfur (sulfonium).
In practice, the cationic surfactant field is dominated by nitrogen
containing compounds, probably because synthetic routes to
nitrogenous cationics are simple and straightforward and give high
yields of product, e.g. they are less expensive.
Cationic surfactants refer to compounds containing at least one
long carbon chain hydrophobic group and at least one positively
charge nitrogen. The long carbon chain group may be attached
directly to the nitrogen atom by simple substitution; or more
preferably indirectly by a bridging functional group or groups in
so-called interrupted alkylamines and amido amines which make the
molecule more hydrophilic and hence more water dispersible, more
easily water solubilized by co-surfactant mixtures, or water
soluble. For increased water solubility, additional primary,
secondary or tertiary amino groups can be introduced or the amino
nitrogen can be quaternized with low molecular weight alkyl groups
further, the nitrogen can be a member of branched or straight chain
moiety of varying degrees of unsaturation; or, of a saturated or
unsaturated heterocyclic ring. In addition, cationic surfactants
may contain complex linkages having more than one cationic nitrogen
atom.
The surfactant compounds classified as amine oxides, amphoterics
and zwitterions are themselves cationic in near neutral to acidic
pH solutions and overlap surfactant classifications.
Polyoxyethylated cationic surfactants behave like nonionic
surfactants in alkaline solution and like cationic surfactants in
acidic solution. The simplest cationic amines, amine salts and
quaternary ammonium compounds. The majority of large volume
commercial cationic surfactants can be subdivided into four major
classes and additional sub-groups including Alkylamines (and
salts), Alkyl imidazolines, Ethoxylated amines and Quaternaries
including Alkyl benzyl-dimethylammonium salts, Alkyl benzene salts,
Heterocyclic ammonium salts, Tetra alkylammonium salts, etc.
As utilized in this invention, cationics are specialty surfactants
incorporated for specific effect; for example, detergency in
compositions of or below neutral pH; antimicrobial efficacy;
thickening or gelling in cooperation with other agents; and so
forth.
Ampholytic surfactants can be broadly described as derivatives of
aliphatic secondary and tertiary amines, in which the aliphatic
radical may be straight chain or branched and wherein one of the
aliphatic substituents contains from about 8 to 18 carbon atoms and
one contains an anionic water solubilizing group, e.g., carboxy,
sulfo, sulfato, phosphato, or phosphono. Amphoteric surfactants are
subdivided into two major classes: (taken from "Surfactant
Encyclopedia" Cosmetics & Toiletries, Vol. 104 (2) 69-71
(1989). Include Acyl/dialkyl ethylenediamine derivatives (2-alkyl
hydroxyethyl imidazoline derivatives) (and salts), N-alkylamino
acids (and salts), 2-alkyl hydroxyethyl imidazoline, etc.
Commercial amphoteric surfactants are derivatized by subsequent
hydrolysis and ring-opening of the imidazoline ring by
alkylation--for example with chloroacetic acid or ethyl acetate.
During alkylation, one or two carboxyalkyl groups react to form a
tertiary amine and an ether linkage with differing alkylating
agents yielding different tertiary amines.
Commercially prominent imidazoline-derived amphoterics include for
example: Cocoamphopropionate, Cocoamphocarboxy-propionate,
Cocoamphoglycinate, Cocoamphocarboxy-glycinate,
Cocoamphopropyl-sulfonate, and Cocoamphocarboxy-propionic acid. The
carboxymethylated compounds (glycinates) listed above frequently
are called betaines. Betaines are a special class of amphoteric
discussed in the section entitled, Zwitterion Surfactants. Long
chain N-alkylamino acids are readily prepared by reaction RNH.sub.2
(R.dbd.C.sub.8 -C.sub.18) fatty amines with halogenated carboxylic
acids. Alkylation of the primary amino groups of an amino acids
leads to secondary and tertiary amines. Alkyl substituents may have
additional amino groups that provide more than one reactive
nitrogen center. Most commercial N-alkylamine acids are alkyl
derivatives of beta-alanine or beta-N(2-carboxyethyl) alanine.
Examples of commercial N-alkylamino acid ampholytes having
application in this invention include alkyl beta-amino
dipropionates, RN(C.sub.2 H.sub.4 COOM).sub.2 and RNHC.sub.2
H.sub.4 COOM. R is an acyclic hydrophobic group containing from
about 8 to about 18 carbon atoms, and M is a cation to neutralize
the charge of the anion.
The following table sets forth the formulations currently in
development.
TABLE 1 ______________________________________ Concentrate
Formulations Raw Material Useful Preferred More Preferred
______________________________________ Phosphoric Acid 0.1%-80.0%
0.1%-60.0% 0.1%-40.0% Organic Acid 0.1%-40.0% 0.1%-20.0% 0.1%-10.0%
Hydrocarbon or Ether 0.1%-40.0% 0.1%-20.0% 0.1%-10.0% Solvent
Sequestrant 0.1%-40.0% 0.1%-20.0% 0.1%-10.0% Ether Amine or
Quaternary 0.1%-40.0% 0.1%-20.0% 0.1%-10.0% Ammonium Salt Water
0.1%-80.0% 0.1%-40.0% 0.1%-80.0%
______________________________________ Use solutions are typically
prepared by dilution with water resulting in an active
concentration of about 100 ppm to about 20,000 ppm.
TABLE 2
__________________________________________________________________________
EXAMPLES 1 THROUGH 10 Raw materials.sup.1 #1 #2 #3 #4 #5 #6 #7 #8
#9 #10
__________________________________________________________________________
Dowfax 2A1 6 6 6 6 6 6 6 6 6 6 C10 F.A. 1 1 1 1 1 1 1 1 1 1 Butyl
Carbitol 5 5 5 Butyl 5 5 5 5 5 5 5 Cellosolve Dowanol PM 5 5 5 5
Dowanol DM Pluronic L-65 5.5 Hydroxy 5 5 5 5 5 5 Acetic Acid Phos
Acid 65 65 65 65 65 65 65 65 65 65 (75%) Abil 8852 1 0.5 1 NAS 8RF
2 Lactic Acid 5 5 5 5 (88%) L.C. Dequest 2 2000 Water 18 15 16 17
18 13 10 10 10 6.5 PS 236 Phos 1 Ester BL-330 3 Triton CF-32 3 DMSO
5 LF428 2.5 Total 100.00% 100.00% 100.00% 100.00% 100.00% 100.00%
100.00% 100.00% 100.00% 100.00%
__________________________________________________________________________
.sup.1 See raw materials page for identity.
TABLE 3
__________________________________________________________________________
EXAMPLES 11 THROUGH 20 Raw materials #11 #12 #13 #15 #16 #17 #18
#19 #20
__________________________________________________________________________
Dowfax 2A1 6 6 6 Q372 2.5 2.5 2.5 IPA 99% 5 5 5 5 5 5 Rhodaterge
BCC 5 Bardac LF 2.5 Mirataine ASC 5 5 5 C10 F.A. 1 1 1 Butyl
Carbitol Butyl Cellosolve 5 5 5 5 5 5 5 5 5 Dowanol PM 5 5 5
Dowanol DM Pluronic L-65 3 Hydroxy Acetic 5 Acid Phos Acid (75%) 65
65 65 30 30 30 30 30 30 Abil 8852 1 NAS 8RF Lactic Acid (88%) 5 5 5
5 5 5 L.C. Dequest 2000 1 1 2.5 2.5 2.5 2.5 2.5 2.5 Water 9 6 9 40
45 45 50 50 50
PS 236 Phos Ester BL-330 Triton CF-32 Dehydol TA-30 3 3 PA-10 ether
amine 2.5 PA-14 ether amine 2.5 LF428 3 5 Total 100.00% 95.00%
100.00% 100.00% 100.00% 100.00% 100.00% 100.00% 100.00%
__________________________________________________________________________
TABLE 4 ______________________________________ EXAMPLES 21 THROUGH
27 Raw materials #21 #22 #23 ______________________________________
Q372 5 IPA 99% 5 Rhodaterge BCC Bardac LF Mirataine ASC Butyl
Carbitol Butyl Cellosolve 5 5 10 Pluronic L-65 Hydroxy Acetic Acid
Phos Acid (75%) 30 30 30 Abil 8852 NAS 8RF Lactic Acid (88%) 5 5 5
L.C. Dequest 2000 2.5 2.5 2.5 Water 45 55 50 PA-10 ether amine 2.5
2.5 2.5 PA-14 ether amine LF428 Total 100.00% 100.00% 100.00%
______________________________________
TABLE 5 ______________________________________ RAW MATERIALS DETAIL
______________________________________ Dowfax 2A1 Alkyl diphenyl
oxide sulfonate C10 FA C.sub.10 Fatty acid Butyl Carbitol
2-(2-butoxyethoxy) ethanol Butyl Cellosolve Butoxy ethanol Dowanol
DM Dimethylene glycol methyl ether Dowanol PM Propylene glycol
methyl ether Pluronic L-65 Nonionic Hydroxy Acetic Acid H.sub.3
PO.sub.4 (75% Aqueous) Abil 8852 Silicon nonionic surfactant NAS
8RF Alkyl sulfoniate Lactic Acid (88%) L.C. Dequest 2000
Amino-(trimethylene phosphoric acid) salt PS 236 Phos Ester Alkyl
phosphonate BL 330 Alcohol ethoxylate chlorine capped (3 moles EO)
Triton CF 32 Alcohol ethoxylate DMSO Dimethyl sulfoxide LF428
nonionic multiblock (EO) (PO) surfactant Q372 Dimethyl alkyl benzyl
quaternary ammonium chloride IPA 99% Isopropyl alcohol Rhodaterge
BCC Rhone - Polene nonionic/solvent premix Bardac LF Quat Dimethyl
C.sub.6-12 dialky quaternary ammonium chloride Mirataine ASC
amphoteric amido propyl betaine PA-10 ether amine isohexyloxypropyl
amine PA-14 ether amine isodecyloxypropyl amine
______________________________________
OBJECTIVE
The objective of the analysis was to determine the sanitizing
efficacy of Ex. 19 and Ex. 20 against Staphylococcus aureus ATCC
6538, Escherichia coli ATCC 11229 and a 1:1 mixed inoculum of
yeast.
TEST METHOD
Germicidal and Detergent Sanitizing Action of Disinfectants--Method
AOAC 960.09-Chap. 6, p. 9, sec. 6.303
______________________________________ METHOD PARAMETERS Test
Substance mL of Test mL of Name Diluent Concentration Substance
Diluent ______________________________________ Ex. 19 500 ppm Hard
1.0% 10.0 990.0 Water Ex. 20 500 ppm Hard 1.0% 10.0 990.0 Water
______________________________________
Test Systems: Staphylococcus aureus ATCC 6538
Escherichia coli ATCC 11229
1:1--Yeast Mixture of:
Candida albicans ATCC 18804
Saccharomyces cervisciae ATCC 834
Test Temperature: 25.degree. C.
Exposure Time: 30 minutes and 60 minutes
Neutralizer: Chambers Solution
Dilutions Plated: 10.sup.-1, 10.sup.-3, 10.sup.-5
Subculture Medium: Tryptone Glucose Extract Agar
(cultivation of Bacteria)
Sabouraud Dextrose Agar (for cultivation of yeast)
Incubation: 37.degree. C. for 48 hours
(for cultivation of bacteria)
26.degree. C. for 72 hours (for cultivation of yeast)
______________________________________ RESULTS
______________________________________ Inoculum Numbers (CFU/mL)
Organism A B Average ______________________________________ E.coli
51 .times. 10.sup.7 55 .times. 10.sup.7 5.3 .times. 10.sup.8 ATCC
11229 S. aureus 132 .times. 10.sup.6 141 .times. 10.sup.6 1.4
.times. 10.sup.8 ATCC 6538 Mixed Yeast 224 .times. 10.sup.4 226
.times. 10.sup.4 2.3 .times. 10.sup.6
______________________________________ Escherichia coli ATCC 11229
Exposure Average Test Times Survivors Survivors Log Percent
Substance (Minutes) (CFU/mL) (CFU/mL) Reduction Reduction
______________________________________ Ex. 19 30 >10.sup.7,
>10.sup.7 >10.sup.7 <1.72 <98.113% Ex. 19 60 20, 21
.times. 10.sup.3 2.0 .times. 10.sup.4 4.42 99.996% Ex. 20 30
<10, <10 <10 >7.72 >99.999% Ex. 20 60 <10, <10
<10 >7.72 >99.999% ______________________________________
Staphylococcus aureus ATCC 6538 Exposure Average Test Times
Survivors Survivors Log Percent Substance (Minutes) (CFU/mL)
(CFU/Ml) Reduction Reduction ______________________________________
Ex. 19 30 >10.sup.7, >10.sup.7 >10.sup.7 <1.15
<92.850% Ex. 19 60 >10.sup.5, 665 .times. 3.3 .times.
10.sup.7 0.63 76.429% 10.sup.5 Ex. 20 30 <10, <10 <10
>7.15 >99.999% Ex. 20 60 <10, <10 <10 >7.15
>99.999% ______________________________________ Mixed Yeast
inoculum of Candida albicans ATCC 18804 and Saccharomyces
cervisciae ATCC 834 Exposure Average Test Times Survivors Survivors
Log Percent Substance (Minutes) (CFU/mL) (CFU/mL) Reduction
Reduction ______________________________________ Ex. 19 30 20,386
.times. 10.sup.5 2.0 .times. 10.sup.7 No No Reduction Reduction Ex.
19 60 3,316 .times. 10.sup.5 1.6 .times. 10.sup.7 No No Reduction
Reduction Ex. 20 30 13,531 .times. 10.sup.5 2.7 .times. 10.sup.7 No
No Reduction Reduction Ex. 20 60 <10, <10 <10 >5.36
>99.999% ______________________________________
CONCLUSIONS
A neutralization control test was performed on both test substances
(Ex. 19 and Ex. 20). The Neutralizer, Chambers Solution, was found
to be an effective neutralizer for these products and was not found
to be detrimental to the test systems employed.
Ex. 19, with a 30 minute exposure time at 25.degree. C., achieved
<98.113% percent reduction against Escherichia coli ATCC 11229
and <92.850% against Staphylococcus aureus ATCC 6538. Ex. 19
with a 60 minute exposure time at 25.degree. C. achieved a 99.996%
reduction against Escherichia coli ATCC 11229, a 76.429% reduction
against Staphylococcus aureus ATCC 653 and achieve no percent
reduction against the mixed yeast inoculum with a 30 minute or 60
minute exposure time. Ex. 20 with a 30 minute exposure time at
25.degree. C., achieved a >99.999% against Escherichia coli ATCC
11229 and a >99.999% reduction against Staphylococcus aureus
ATCC 6538. Ex. 20 with a 30 minute exposure time at 25.degree. C.
achieved no percent reduction against the mixed yeast inoculum. Ex.
20 with a 60 minute exposure time at 25.degree. C. achieved a
>99.999% reduction against Escherichia coli ATCC 11229,
Staphylococcus aureus ATCC 653 and the mixed yeast inoculum.
OBJECTIVE
The objective of the analysis was to determine the food contact
surface sanitizing efficacy of Ex. 16 and Ex. 17 against
Staphylococcus aureus ATCC 6538 and Escherichia coli ATCC
11229.
TEST METHOD
Germicidal and Detergent Sanitizing Action of Disinfectants--Method
AOAC 960.09-Chap. 6, p.9, sec. 6.303
______________________________________ METHOD PARAMETERS Test mL of
Substance Test Sub- Name Diluent Conc stance mL of Diluent
______________________________________ Ex. 16 500 ppm synthetic
0.50% 2.5 Volume brought hard water to 500 mL Ex. 16 500 ppm
synthetic
1.0% 5.0 Volume brought hard water to 500 mL Ex. 17 500 ppm
synthetic 0.50% 2.5 Volume brought hard water to 500 mL Ex. 17 500
ppm synthetic 1.0% 5.0 Volume brought hard water to 500 mL
______________________________________
Test Systems: Staphylococcus aureus ATCC 6538
Escherichia coli ATCC 11229
Test Temperature: room temperature
Exposure Time: 15 and 30 minutes
Neutralizer: Chambers
Subculture Medium: Tryptone Glucose Extract Agar
Incubation: 37.degree. C. for 48 hours
______________________________________ RESULTS:
______________________________________ Inoculum Numbers (CFU/mL)
Organism A B C Average ______________________________________ S.
aureus 132 .times. 10.sup.6 96 .times. 10.sup.6 118 .times.
10.sup.6 1.2 .times. 10.sup.8 ATCC 6538 E. coli 145 .times.
10.sup.6 156 .times. 10.sup.6 121 .times. 10.sup.6 1.4 .times.
10.sup.8 ATCC 11229 ______________________________________
Staphylococcus aureus ATCC 6538 Test Average Percent Sub- Time
Survivors Survivors Log Reduc- stance Conc. point (CFU/mL) (CFU/mL)
R tion ______________________________________ Ex. 16 0.50% 15 min.
41 .times. 10.sup.3 2.1 .times. 10.sup.4 3.76 99.983 42 .times.
10.sup.1 Ex. 16 0.50% 30 min. 33, 34 .times. 10.sup.1 3.4 .times.
10.sup.2 5.55 99.999 Ex. 16 1.0% 15 min. 40, 34 .times. 10.sup.1
3.7 .times. 10.sup.2 5.51 99.999 Ex. 16 1.0% 30 min. 28, 31 .times.
10.sup.1 3.0 .times. 10.sup.2 5.60 99.999 Ex. 17 0.50% 15 min. 136,
138 .times. 10.sup.5 1.4 .times. 10.sup.7 0.93 88.333 Ex. 17 0.50%
30 min. 49, 43 .times. 10.sup.1 4.6 .times. 10.sup.6 1.42 96.167
Ex. 17 1.0% 15 min. 320 .times. 10.sup.1 2.2 .times. 10.sup.4 3.74
99.982 40 .times. 10.sup.3 Ex. 17 1.0% 30 min. 30, 37 .times.
10.sup.1 3.4 .times. 10.sup.2 5.55 99.999
______________________________________ Escherichia coli ATCC 11229
Test Average Percent Sub- Time Survivors Survivors Log Reduc-
stance Conc. point (CFU/mL) (CFU/mL) R tion
______________________________________ Ex. 16 0.50% 15 min. 32, 26
.times. 10.sup.1 2.9 .times. 10.sup.2 5.68 99.999 Ex. 16 0.50% 30
min. 30, 30 .times. 10.sup.1 3.0 .times. 10.sup.2 5.67 99.999 Ex.
16 1.0% 15 min. 33, 36 .times. 10.sup.1 3.5 .times. 10.sup.2 5.60
99.999 Ex. 16 1.0% 30 min. 30, 33 .times. 10.sup.1 3.2 .times.
10.sup.2 5.64 99.999 Ex. 17 0.50% 15 min. 29, 36 .times. 10.sup.1
3.3 .times. 10.sup.2 5.63 99.999 Ex. 17 0.50% 30 min. 37, 33
.times. 10.sup.1 3.5 .times. 10.sup.2 5.60 99.999 Ex. 17 1.0% 15
min. 32, 32 .times. 10.sup.1 3.2 .times. 10.sup.2 5.64 99.999 Ex.
17 1.0% 30 min. 28, 29 .times. 10.sup.1 2.9 .times. 10.sup.2 5.68
99.999 ______________________________________
A neutralization test was performed. The test substances were
effectively neutralized and Chambers was observed to not be
detrimental to the cells.
CONCLUSIONS
Ex. 16 achieved >99.999 percent reduction against Staphylococcus
aureus ATCC 6538 at all time points except 0.50% at 15 minutes.
However, one plate from this sample showed counts in the 10.sup.1
range and the other in the 10.sup.3 range. This result should be
confirmed. Ex. 16 was efficacious against Escherichia coli ATCC
11229 at all concentrations and time points.
Ex. 17 achieved >99.999 percent reduction against Staphylococcus
aureus ATCC 6538 only at a concentration of 1% with a 30 minute
exposure time. It was efficacious against Escherichia coli ATCC
11229 at all concentrations and time points.
Cleaning Characteristics
Method
Used 2.0% solution, 30 min concentration, start 5.degree.
C.--finish 10-12.degree. C., 500 rpm w/11/2 stir bar.
Formulas #1-#14: Removed some soil with limited removal of
fermentation ring
Formula #15, #16 and #18: Removed 95-99% of fermentation ring soil;
some yeast spots remain; performance equal or better than
commercial product Trimeta HC (a phosphonate, phosphoric acid and
nonionic surfacant blend). This product cleaned well but had little
or no antimicrobial properties.
Formula #17: 80% removal of fermentation ring. Spots of yeast
remaining
Formula #19: Better than #1 through #14, but removed 70%+ of
fermentation ring.
Foam Profiles on Cleaners
The foaming characteristics of comparative compositions and the
compositions of the invention were tested. The cylinder foam test:
used. One hundred milliliters of test solution (concentration in
table below); were tested. In the procedure, 10 inversions were
conducted at ambient (room. Temp). in deionized. water. The test
apparatus was a 250 ml graduated cylinder. The formulae,
particularly Examples 16 through 20 exhibited excellent low foam
characteristics.
______________________________________ Test Formula was Example 15
1.0% 2.0% Time (min) Foam (ml) Time (min) Foam (ml) Soln Temp
______________________________________ 0 50 0 50 22.degree. C. 1 45
1 45 3 40 3 45 5 40 5 40 ______________________________________
______________________________________ Test Formula was Example 16
1.0% 2.0% Time (min) Foam (ml) Time (min) Foam (ml) Soln Temp
______________________________________ 0 60 0 90 22.degree. C. 1 60
1 88 3 50 3 80 5 45 5 60 ______________________________________
______________________________________ Test Formula was Example 17
1.0% 2.0% Time (min) Foam (ml)
______________________________________ 0 35 0 50 1 15 1 30 3 10 3
10 5 10 5 ______________________________________
______________________________________ Test Formula was Example 18
1.0% 2.0% Time (min) Foam (ml) Time (min) Foam (ml)
______________________________________ 0 60 0 60 1 20 1 30 3 15 3
15 5 10 5 10 ______________________________________
______________________________________ Test Formula was Example 19
1.0% 2.0% Time (min) Foam (ml) Time (min) Foam (ml)
______________________________________ 0 15 0 20 1 2 1 2 3 2 3 2 5
2 5 2 ______________________________________
______________________________________ Test Formula was Example 20
1.0% 2.0% Time (min) Foam (ml) Time (min) Foam (ml)
______________________________________ 0 15 0 20 1 2 1 2 3 2 3 2 5
2 5 2 ______________________________________
The forgoing specification examples and data serve to explain the
aspects of the invention identified to date. The invention can
comprise a variety of compositions methods and embodiments without
departing from the spirit and scope of the invention. The invention
is found in the claims hereinafter appended.
* * * * *